Process for making cathode materials for lithium ion batteries

ABSTRACT

Li 1+x (Ni a Co b Mn c M d ) 1−x O 2    (I)
 
     Process for making a particulate material of general formula (I), wherein the integers are defined as follows: M is selected from Al and Ti, x is in the range of from 0.015 to 0.03, a is in the range of from 0.3 to 0.6, b is in the range of from 0.05 to 0.35, c is in the range of from 0.2 to 0.5, d is in the range of from 0.001 to 0.03, with a+b+c+d=1 said process comprising the following steps: (a) co-precipitating a mixed hydroxide of nickel, cobalt and manganese from a solution of water-soluble salts of nickel, cobalt and manganese by contacting such solution with a solution of alkali metal hydroxide, (b) adding an aqueous solution of an aluminate or titanate and thereby co-precipitating a layer of a mixed hydroxide of nickel and cobalt and manganese and aluminium or titanium on the particles formed in step (a), (c)removing particles of (Ni a  Co b  Mn c  Al d )(OH) 2+d  or (Ni a  Co b  Mn c  Ti d )(OH) 2−2d  so obtained and drying them in the presence of oxygen, (d) mixing the particles obtained in step (c) with at least one Li compound selected from Li 2 O, LiOH and Li 2 CO 3 , (e) calcining the mixture obtained according to step (d) at a temperature in the range of from 920 to 950° C.

Process for Making Cathode Materials for Lithium Ion Batteries

The present invention is directed towards a process for making aparticulate material of general formula (I),

Li_(1+x)(Ni_(a)Co_(b)Mn_(c)Al_(d))_(1−x)O₂   (I)

wherein

x is in the range of from 0.015 to 0.03,

a is in the range of from 0.3 to 0.6,

b is in the range of from 0.05 to 0.35,

c is in the range of from 0.2 to 0.5,

d is in the range of from 0.001 to 0.03,

with a+b+c+d=1

said process comprising the following steps:

-   -   (a) co-precipitating a mixed hydroxide of nickel, cobalt and        manganese from a solution of water-soluble salts of nickel,        cobalt and manganese by contacting such solution with a solution        of alkali metal hydroxide,    -   (b) adding an aqueous solution of an aluminate and thereby        co-precipitating a layer of a mixed hydroxide of nickel and        cobalt and manganese and aluminium on the particles formed in        step (a),    -   (c) removing particles of (Ni_(a)Co_(b)Mn_(c)Al_(d))(OH)_(2+d)        so obtained and drying them in the presence of oxygen,    -   (d) mixing the particles obtained in step (c) with at least one        Li compound selected from Li₂O, LiOH and Li₂CO₃,    -   (e) calcining the mixture obtained according to step (d) at a        temperature in the range of from 920 to 950° C.

Furthermore, the present invention is directed to particulate materialsand their use in lithium ion batteries.

Lithiated transition metal oxides with layered structures are currentlybeing used as electrode materials for lithium-ion batteries. Extensiveresearch and developmental work has been performed in the past years toimprove properties like charge density, energy, but also otherproperties like the reduced cycle life and capacity loss that mayadversely affect the lifetime or applicability of a lithium-ion battery.

In a usual process for making cathode materials for lithium-ionbatteries, first a so-called precursor is being formed byco-precipitating the transition metals as carbonates, oxides orpreferably as hydroxides that may or may not be basic. The precursor isthen mixed with a lithium salt such as, but not limited to LiOH, Li₂O,LiNO₃ or—especially—Li₂CO₃ followed by calcination.

When used in means for propulsion, for example aircrafts or vehicles,batteries have to meet very high safety standards. The safetyrequirements do not only refer to dependability under conditions likeelevated temperature but also to inflammability and oxidizing behavior.Many batteries are being tested by the nail test—a nail is being driventhrough the battery and the behavior is observed—and under other extremeconditions.

Most lithium ion batteries contain an electrolyte that is based on oneor more organic solvents that are inflammable. Reactions of the cathodeactive material with the electrolyte are of key relevance, and, inparticular, exothermic reactions need to be studied. A commonly usedtest for studying potential reactions of the cathode active materialwith the electrolyte is the determination of the onset temperature bydifferential scanning calorimetry (DSC) performed on electrochemicalcells or on their key components, especially on a combination of theircathode active material and the electrolyte.

Many measures can be considered to improve the safety behavior oflithium ion batteries. Flame-retardant additives for the electrolytehave been suggested, amendment of the set-up of the battery, andimprovement of one or more of the components of the battery such asanode or—in particular—cathode active material. However, the solutionssuggested so far still leave room for improvement.

It was an objective of the present invention to provide electrochemicalcells with an improved safety performance. It was further an objectiveof the present invention to provide components for electrochemical cellsthat help to improve the safety performance of electrochemical cells. Itwas further an objective of the present invention to provide a methodfor making components for electrochemical cells that help to improve thesafety performance of electrochemical cells.

Accordingly, the process as defined at the outset has been found,hereinafter also referred to as inventive process or process accordingto the present invention.

The inventive process refers to a process for making a particulatematerial of general formula (I)

Li_(1+x)(Ni_(a)Co_(b)Mn_(c)M_(d))_(1−x)O₂   (I)

wherein

x is in the range of from 0.015 to 0.03,

a is in the range of from 0.3 to 0.6,

b is in the range of from 0.05 to 0.35, preferably from 0.15 to 0.25,

c is in the range of from 0.2 to 0.5, preferably up to 0.35,

d is in the range of from 0.001 to 0.03, preferably 0.01 to 0.03,

with a+b+c+d=1.

In one embodiment of the present invention, b is in the range of from0.15 to 0.25 and c is in the range of from 0.2 to 0.35, with a+b+c+d=1.

The term “particulate” in the context with material of general formula(I) shall mean that said material is provided in the form of particleswith a maximum particle diameter not exceeding 32 μm. Said maximumparticle diameter can be determined by, e.g. sieving.

In one embodiment of the present invention, the particulate material ofgeneral formula (I) is comprised of spherical particles, that areparticles have a spherical shape. Spherical particles shall include notjust those which are exactly spherical but also those particles in whichthe maximum and minimum diameter of at least 90% (number average) of arepresentative sample differ by not more than 10%.

In one embodiment of the present invention, the particulate material ofgeneral formula (I) is comprised of secondary particles that areagglomerates of primary particles. Preferably, the particulate materialof general formula (I) is comprised of spherical secondary particlesthat are agglomerates of primary particles. Even more preferably, theparticulate material of general formula (I) is comprised of sphericalsecondary particles that are agglomerates of spherical primary particlesor platelets.

In one embodiment of the present invention, the mean particle diameter(D50) of secondary particles of material of general formula (I) is inthe range of from 6 to 12 μm, preferably 7 to 10 μm. The mean particlediameter (D50) in the context of the present invention refers to themedian of the volume-based particle diameter, as can be determined, forexample, by light scattering.

In one embodiment of the present invention, primary particles ofparticulate material of general formula (I) have an average diameter inthe range from 1 to 2000 nm, preferably from 10 to 1000 nm, particularlypreferably from 50 to 500 nm. The average primary particle diameter can,for example, be determined by SEM or TEM. SEM is an abbreviation ofscanning electron microscopy, TEM is an abbreviation of transmissionelectron microscopy

The inventive process comprises the following steps:

-   -   (a) co-precipitating a mixed hydroxide of nickel, cobalt and        manganese from a solution of water-soluble salts of nickel,        cobalt and manganese by contacting such solution with a solution        of alkali metal hydroxide,    -   (b) adding an aqueous solution of an aluminate and thereby        co-precipitating a layer of a mixed hydroxide of nickel and        cobalt and manganese and aluminium on the particles formed in        step (a),    -   (c) removing particles of (Ni_(a)Co_(b)Mn_(c)Al_(d))(OH)_(2+d)        so obtained and drying them in the presence of oxygen,    -   (d) mixing the particles obtained in step (c) with at least one        Li compound selected from Li₂O, LiOH and Li₂CO₃,    -   (e) calcining the mixture obtained according to step (d) at a        temperature in the range of from 920 to 950° C.

The above steps (a) to (e) will be explained in more detail below.

Steps (a) to (e) of the inventive process are being performed in theorder step (a), step (b), step (c), step (d) and step (e). They may beperformed consecutively without substantial intermediate steps, or theymay be performed with one or more intermediate steps.

Said mixed hydroxide of nickel, cobalt and manganese may, comprisecounterions other than hydroxide, for example carbonate, sulfate,nitrate, carboxylate, especially acetate, or halide, especiallychloride. A particularly preferred counterion, apart from hydroxide, isoxide, especially in combination with sulfate. It is possible forcarbonate, sulfate, carboxylate or halide to be present in traces inmixed transition hydroxide of nickel, cobalt and manganese, for exampleof up to 1% by weight, based on hydroxide. Oxide may be present ingreater proportions in mixed hydroxide of nickel, cobalt and manganese;for example, every tenth anion may be an oxide ion.

Said mixed hydroxide of nickel, cobalt and manganese may contain tracesof other metal ions, for example traces of ubiquitous metals such assodium, Ca or Zn, but such traces will not be taken into account in thedescription of the present invention. Traces in this context will meanamounts of 0.5 mol-% or less, referring to the total metal content ofsaid mixed hydroxide of nickel, cobalt and manganese.

In step (a) of the inventive process, a solution containingwater-soluble salts of nickel, cobalt and manganese is contacted with asolution of alkali metal hydroxide. An example of alkali metalhydroxides is lithium hydroxide, preferred is potassium hydroxide andeven more preferred is sodium hydroxide.

Said contacting can be performed by simultaneously feeding a solution ofalkali metal hydroxide and one or more solutions of water-soluble saltsof nickel, cobalt and manganese into a vessel, preferably understirring. It is preferred to perform such contacting by feeding asolution of alkali metal hydroxide and a solution containingwater-soluble salts of each cobalt, nickel and manganese, in the molarratio of said material of general formula (I).

Water-soluble in the context of the present invention shall mean thatsuch salt has a solubility of at least 20 g/l in distilled water at 20°C., the amount of salt being determined under omission of crystal waterand of water stemming from aquo complexes. Water-soluble salts ofnickel, cobalt and manganese may preferably be the respectivewater-soluble salts of Ni²⁺, Co²⁺, and Mn²⁺.

In one embodiment of the present invention, the step (a) of theinventive process is performed at temperatures in the range from 10 to85° C., preferably at temperatures in the range from 20 to 60° C.

In one embodiment of the present invention, step (a) of the inventiveprocess is performed at a pH value in the range from 8 to 12, preferably10.5 to 12.0, more preferably 11.3 to 11.9, each measured in the motherliquor at 23° C.

In one embodiment of the present invention, the inventive process isperformed at a pressure in the range from 500 mbar to 20 bar, preferablystandard pressure.

In one embodiment of the present invention, an excess of precipitant isused, for example alkali metal hydroxide, based on transition metal. Themolar excess may, for example, be in the range from 1.1:1 to 100:1. Itis preferable to work with a stoichiometric proportion of precipitant.

In one embodiment of the present invention, aqueous solution of alkalimetal hydroxide has a concentration of alkali metal hydroxide in therange from 1 to 50% by weight, preferably 10 to 25% by weight.

In one embodiment of the present invention, the concentrations ofaqueous solution of nickel, cobalt, and manganese salts can be selectedwithin wide ranges. Preferably, the concentrations are selected suchthat they are within the range of, in total, 1 to 1.8 mol of thetransition metals/kg of solution, more preferably 1.5 to 1.7 mol of thetransition metals/kg of solution. “The transition metal salts” usedherein refers to the water-soluble salts of nickel, cobalt andmanganese.

In one embodiment of the present invention, step (a) of the inventiveprocess is performed in the presence of at least one compound L whichmay serve as a ligand for at least one of the transition metals, forexample in the presence of at least one organic amine or especially ofammonia. In the context of the present invention, water should not beregarded as a ligand.

In one embodiment of the present invention, a concentration of L,especially of ammonia, within the range from 0.05 to 1 mol/l, preferably0.1 to 0.7 mol/l, is selected. Particular preference is given to amountsof ammonia for which the solubility of Ni²⁺ in the mother liquor is notmore than 1000 ppm, more preferably not more than 500 ppm.

In one embodiment of the present invention, mixing is effected duringstep (a) of the inventive process, for example with a stirrer.Preference is given to introducing a stirrer output of at least 1 W/linto the reaction mixture, preferably at least 3 W/l and more preferablyat least 5 W/l. In one embodiment of the present invention, a stirreroutput of not more than 25 W/l can be introduced into the reactionmixture.

In a specific embodiment of the present invention, the procedure may be,in the case of batchwise process variants, to lower the stirrer outputtoward the end in batchwise operations.

In one embodiment of the present invention, mother liquor is drawn offduring carrying out step (a) of the inventive process.

Step (a) of the inventive process can be performed in the presence orabsence of one or more reducing agents. Examples of suitable reducingagents are hydrazine, ascorbic acid, glucose and alkali metal sulfites.It is preferable not to use any reducing agent in step (a).

Step (a) of the inventive process can be performed under air, underinert gas atmosphere, for example under noble gas or nitrogenatmosphere, or under reducing atmosphere. An example of a reducing gasis, for example, SO₂. Preference is given to working under inert gasatmosphere.

Step (a) of the inventive process furnishes a mixed hydroxide of nickel,cobalt, and manganese in the form of particles that are slurried intheir mother liquor. Said particles may have an irregular or preferablea spherical shape. Spherical particles shall include not just thosewhich are exactly spherical but also those particles in which themaximum and minimum diameter of at least 95% (number average) of arepresentative sample differ by not more than 5%.

In one embodiment of the present invention, step (a) has a duration of 1to 40 hours, preferably of 2 to 30 hours.

In one embodiment of the present invention, each aqueous solution ofwater-soluble salts of nickel, cobalt and manganese on one hand and ofsolution of alkali metal hydroxide on the other hand are added at aconstant rate, and aqueous solution of water-soluble salts of nickel,cobalt and manganese has a constant composition. In this embodiment, thedistribution of the transition metals nickel, cobalt and manganese inparticles formed in step (a) of the inventive process is homogeneous.

In alternative embodiments, the rates of addition of aqueous solution ofwater-soluble salts of nickel, cobalt and manganese on one hand and ofsolution of alkali metal hydroxide on the other hand are changed duringstep (a) of the inventive process, and/or the composition of the aqueoussolution of water-soluble salts of nickel, cobalt and manganese isaltered during step (a). In the latter embodiment, particles of mixedhydroxides may be obtained in which at least two of the transitionmetals exhibit a concentration gradient.

Step (b) of the inventive process is adding an aqueous solution of analuminate and thereby co-precipitating a layer of a mixed hydroxide ofnickel and cobalt and manganese and aluminium on the particles formed instep (a). The layer co-precipitated in step (b) thus contains a mixedhydroxide of nickel and cobalt and manganese and aluminium. The additionof solution of transition metals and of alkali metal hydroxide iscontinued during step (b).

In the context of the present invention, the term hydroxide of aluminumisused as idealized version of the respective hydroxide. They may alsocontain some oxide or be summarized as Al₂O₃.aq.

Aluminate can be selected from alkali metal aluminate, preferred issodium aluminate, NaAlO₂.

In one embodiment of the present invention, aqueous solution of analuminate has a concentration of from 1 to 300 g Al³⁺/l.

In one embodiment of the present invention, aqueous solution ofaluminate has a pH value about 14.

During the addition of aqueous solution of an aluminate in step (b), theaddition of aqueous solution of water-soluble salts of nickel, cobaltand manganese is usually continued, for example at a reduced rate or aconstant rate compared to step (a) before start of step (b).

During the addition of aqueous solution of an aluminate in step (b), theaddition of solution of alkali metal hydroxide is usually continued, forexample at a reduced rate or a constant rate or a higher rate comparedto step (a) before start of step (b). It is preferred to maintain the pHvalue constant.

In one embodiment of the present invention, the addition of both aqueoussolution of water-soluble salts of nickel, cobalt and manganese andsolution of alkali metal hydroxide is being continued, at a reduced orhigher speed compared to step (a) before start of step (b) or at thesame rate as in step (a) before start of step (b). In embodimentswherein aluminate is added in step (b) the addition of solution ofalkali metal hydroxide is being reduced in step (b). Preferably, the pHvalue is being maintained essentially constant during steps (a) and (b).

In order to avoid side-reactions, it is preferred to add aqueoussolution of aluminate through a different inlet into the vessel in whichstep (a) was commenced.

In one embodiment of the present invention, step (b) has a duration of10 minutes to 8 hours, preferably of 30 minutes to 6 hours. Even morepreferably, step (b) has a duration of 5 to 30% of the duration of step(a).

Step (a) and step (b) are preferably performed in the same vessel.

In a preferred embodiment, step (a) and step (b) may be performed underthe same conditions of pressure, temperature, and stirring.

Step (c) of the inventive process comprises removing particles of(Ni_(a)Co_(b)Mn_(c)Al_(d))(OH)_(2+d) so obtained and drying them in thepresence of oxygen.

Removal of particles of (Ni_(a)Co_(b)Mn_(c)Al_(d))(OH)_(2+d) refers toremoval of said particles from the respective mother liquor. The removalcan be effected, for example, by filtration, centrifugation,decantation, spray drying or sedimentation, or by a combination of twoor more of the aforementioned operations. Suitable apparatuses are, forexample, filter presses, belt filters, spray dryers, hydrocyclones,inclined clarifiers or combinations of the aforementioned apparatuses.

Mother liquor refers to water, water-soluble salts and any furtheradditives present in solution. Possible water-soluble salts are, forexample, alkali metal salts of the counterions of the transition metals,for example sodium acetate, potassium acetate, sodium sulfate, potassiumsulfate, sodium nitrate, potassium nitrate, sodium halide, especiallysodium chloride, potassium halide, and also additional salts, anyadditives used, and any excess alkali metal hydroxide, and also ligandL. In addition, the mother liquor may comprise traces of solubletransition metal salts.

It is desirable to remove the particles as completely as possible.

As with the hydroxides of aluminum, the formula(Ni_(a)Co_(b)Mn_(c)Al_(d))(OH)_(2+d) is to be viewed as idealizedformulae.

After the actual removal, the particles of(Ni_(a)Co_(b)Mn_(c)Al_(d))(OH)_(2+d) can be washed. Washing can beeffected, for example, with pure water or with an aqueous solution ofalkali metal carbonate or alkali metal hydroxide, especially with anaqueous solution of sodium carbonate, potassium carbonate, sodiumhydroxide, potassium hydroxide or ammonia. Water and aqueous solution ofalkali metal hydroxide, especially of sodium hydroxide, are preferred.

The washing can be effected, for example, with employment of elevatedpressure or elevated temperature, for example 30 to 50° C. In anothervariant, the washing is performed at room temperature. The efficiency ofthe washing can be checked by analytical measures. For example, thecontent of transition metal(s) in the washing water can be analyzed.

If washing is effected with water rather than with an aqueous solutionof alkali metal hydroxide, it is possible to check with the aid ofconductivity studies on the washing water whether water-solublesubstances, for example water-soluble salts, can still be washed out.

After removal, the particles of (Ni_(a)Co_(b)Mn_(c)Al_(d))(OH)_(2+d) or(Ni_(a)Co_(b)Mn_(c)Ti_(d))(OH)_(2+2d) are dried in the presence ofoxygen. Presence of oxygen in this context refers to the presence ofoxygen gas. Presence of oxygen therefore includes an atmosphere of air,of pure oxygen, of mixtures from oxygen with air, and of air dilutedwith an inert gas such as nitrogen.

The drying can be performed, for example, at a temperature in the rangefrom 30 to 150° C. If the drying is performed with air, it is observedin many cases that some transition metals are partially oxidized, forexample Mn²⁺ to Mn⁴⁺ and Co²⁺ to Co³⁺, and blackening of the particles(Ni_(a)Co_(b)Mn_(c)Al_(d))(OH)_(2+d) or(Ni_(a)Co_(b)Mn_(c)Ti_(d))(OH)_(2+2d) is observed.

To perform step (d) of the inventive process, the procedure may be, forexample, to mix particles obtained in step (c) with at least one lithiumcompound selected from Li₂O, LiOH and Li₂CO₃, water of crystallizationbeing neglected in the context of the present invention. Preferredsource of lithium is Li₂CO₃.

To perform step (d) of the inventive process, the amounts of particlesobtained in step (c) and lithium compound are selected so as to obtainthe stoichiometry of the desired material of formula (I). Preferably,particles obtained in step (c) and lithium compound(s) are selected suchthat the molar ratio of lithium to the sum of all transition metals andany M is in the range from 1.015:1 to 1.03:1, preferably 1.03:1 to1.08:1, even more preferably 1.04:1 to 1.07:1.

To perform step (e) of the inventive process, the mixture obtainedaccording to step (d) is being calcined at a temperature in the range offrom 920 to 950° C.

Step (e) of the inventive process can be performed in a furnace, forexample in a rotary tube furnace, in a muffle furnace, in a pendulumfurnace, in a roller hearth furnace or in a push-through furnace.Combinations of two or more of the aforementioned furnaces are possibleas well.

Step (e) of the inventive process can be performed over a period of 30minutes to 24 hours, preferably 3 to 12 hours. Step (e) can be effectedat a temperature level, or a temperature profile can be run.

In one embodiment of the present invention, step (e) is being performedin an oxygen-containing atmosphere. Oxygen-containing atmosphereincludes an atmosphere of air, of pure oxygen, of mixtures from oxygenwith air, and of air diluted with an inert gas such as nitrogen. In step(e), preferred is an atmosphere of oxygen or oxygen diluted with air ornitrogen and a minimum content of oxygen of 21 vol.-%.

In one embodiment of the present invention, between steps (d) and (e) atleast one precalcining step (e*) is being performed. Step (e*) comprisesheating the mixture obtained in step (d) at a temperature in the rangeof from 300 to 700° C. for a period of 2 to 24 hours, and performingstep (e) with the material obtained in step(s) (e*).

In one embodiment of the present invention, two pre-calcining steps arebeing performed between steps (d) and (e). Said two pre-calcining stepsinclude heating the mixture obtained in step (d) at a temperature in therange of from 300 to 400° C. for a period of 2 to 12 hours, followed byheating the material so obtained at a temperature in the range of from500 to 700° C. for a period of 2 to 12 hours.

During the temperature changes, a heating rate of 1 K/min up to 10 K/mincan be obtained, preferred is 2 to 5 K/min.

During step (e), the hydroxide precursor is converted into particulatematerial of general formula (I). Without wishing to be bound by anytheory, during step (e) the Al³⁺-cations or the Ti⁴⁺ cations,respectively, may diffuse freely within the particles. Transition metalions diffuse much slower if at all.

After having performed step (e) of the inventive process, a particulatematerial according to formula (I) is obtained. Additional steps may beperformed, such as cooling down the particulate material, or sieving inorder to remove agglomerates with a particles diameter of more than 32μm.

The particulate material obtained according to the inventive process iswell suited as cathode active material. It combines good electrochemicalbehavior with a high onset temperature.

Another aspect of the present invention is a cathode active material,hereinafter also being referred to as “particulate material according toformula (I)”, for a lithium ion battery, essentially consisting ofparticles of general formula (I)

Li_(1+x)(Ni_(a)Co_(b)Mn_(c)M_(d))_(1−x)O₂   (I)

wherein

x is in the range of from 0.015 to 0.03,

a is in the range of from 0.3 to 0.6,

b is in the range of from 0.05 to 0.35, preferably from 0.15 to 0.25,

c is in the range of from 0.2 to 0.5, preferably up to 0.35,

d is in the range of from 0.001 to 0.03, preferably 0.01 to 0.03,

with a+b+c+d=1,

having an average particle diameter (D50) in the range of from 5 to 12μm, wherein Al is homogeneously dispersed within said particles. In thecontext of the present invention, average particle diameter and meanparticle diameter are used interchangeably.

One way to determine whether Al is homogeneously dispersed in particlesof particulate material according to formula (I) is by SEM/EDX mapping.

In one embodiment of the present invention, b is in the range of from0.15 to 0.25 and c is in the range of from 0.2 to 0.35, with a+b+c+d=1.

In one embodiment of the present invention, the onset temperature (DSC)of cathode active material according to the present invention is in therange of from 305° C. to 320° C., wherein said onset temperature isadvantageously measured by differential scanning calorimetry (DSC). Theonset temperature is advantageously determined as follows: therespective cathode material is first tested in an electrochemical cell.After having gone through a cycling program and after charging to acertain but identical voltage, the electrochemical cell is beingdisassembled, and the cathode composition is being removed from thecurrent collector mechanically. It is then mixed with an electrolyte,preferably in a 1 M solution of LiPF₆ in a mixture of organiccarbonates. Then, the resultant slurry is subjected to a differentialscanning calorimetry (DSC) measurement. The onset temperature can bedetermined from the DSC measurement directly.

The inventive cathode active material essentially consists of particlesgeneral formula (I). In the context of the present invention, that meansthat the inventive cathode active material does not contain separateAl₂O₃ particles, determined by SEM or EDX or a combination of EDX andSEM. In the context of the present invention, “essentially consisting ofparticles of general formula (I) shall include cathode active materialsthat contain less than 1 separate particle of Al₂O₃ per 100 particles ofcompound of general formula (I). Even more preferably, cathode materialsaccording to the present invention do not contain detectable amounts ofAl₂O₃ particles.

In one embodiment of the present invention inventive cathode activematerial contains in the range of from 0.01 to 2% by weight Li₂CO₃,determined as Li₂CO₃ and referring to said cathode active material.

In one embodiment of the present invention, the surface (BET) ofinventive cathode active material is in the range of from 0.2 to 10m²/g, preferably from 0.3 to 1 m²/g. The surface (BET) can be determinedby nitrogen absorption, for example according to DIN 66131.

Inventive cathode active material may in particular serve as electrodematerial, especially for cathodes for lithium ion batteries.

A further aspect of the present invention are electrodes comprising atleast one inventive cathode active material. They are particularlyuseful for lithium ion batteries. Lithium ion batteries comprising atleast one electrode according to the present invention exhibit a verygood discharge and cycling behavior, and they show good safety behavior.

In one embodiment of the present invention, inventive cathodes contain

-   -   (A) at least one cathode active material, as described above,    -   (B) carbon in an electrically conductive state, and    -   (C) a binder,    -   (D) a current collector.

In a preferred embodiment of the present invention, inventive cathodescontain

-   -   (A) 80 to 95% by weight cathode active material,    -   (B) 3 to 17% by weight of carbon,    -   (C) 3 to 10% by weight of binder material,

percentages referring to the sum of (A), (B) and (C).

Cathodes according to the present invention contain carbon inelectrically conductive modification, in brief also referred to ascarbon (B). Carbon (B) can be selected from soot, active carbon, carbonnanotubes, graphene, and graphite. Carbon (B) can be added as suchduring preparation of electrode materials according to the invention.

Electrodes according to the present invention can comprise furthercomponents. They can comprise a current collector (D), such as, but notlimited to, an aluminum foil. They further comprise a binder material(C), hereinafter also referred to as binder (C). Current collector (D)is not further described here.

Suitable binders (C) are preferably selected from organic (co)polymers.Suitable (co)polymers, i.e. homopolymers or copolymers, can be selected,for example, from (co)polymers obtainable by anionic, catalytic orfree-radical (co)polymerization, especially from polyethylene,polyacrylonitrile, polybutadiene, polystyrene, and copolymers of atleast two comonomers selected from ethylene, propylene, styrene,(meth)acrylonitrile and 1,3-butadiene. Polypropylene is also suitable.Polyisoprene and polyacrylates are additionally suitable. Particularpreference is given to polyacrylonitrile.

In the context of the present invention, polyacrylonitrile is understoodto mean not only polyacrylonitrile homopolymers but also copolymers ofacrylonitrile with 1,3-butadiene or styrene. Preference is given topolyacrylonitrile homopolymers.

In the context of the present invention, polyethylene is not onlyunderstood to mean homopolyethylene, but also copolymers of ethylenewhich comprise at least 50 mol % of copolymerized ethylene and up to 50mol % of at least one further comonomer, for example a-olefins such aspropylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene,1-dodecene, 1-pentene, and also isobutene, vinylaromatics, for examplestyrene, and also (meth)acrylic acid, vinyl acetate, vinyl propionate,C₁-C₁₀-alkyl esters of (meth)acrylic acid, especially methyl acrylate,methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butylacrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, 2-ethylhexylmethacrylate, and also maleic acid, maleic anhydride and itaconicanhydride. Polyethylene may be HDPE or LDPE.

In the context of the present invention, polypropylene is not onlyunderstood to mean homopolypropylene, but also copolymers of propylenewhich comprise at least 50 mol % of copolymerized propylene and up to 50mol % of at least one further comonomer, for example ethylene andα-olefins such as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecene and1-pentene. Polypropylene is preferably isotactic or essentiallyisotactic polypropylene.

In the context of the present invention, polystyrene is not onlyunderstood to mean homopolymers of styrene, but also copolymers withacrylonitrile, 1,3-butadiene, (meth)acrylic acid, C₁-C₁₀-alkyl esters of(meth)acrylic acid, divinylbenzene, especially 1,3-divinylbenzene,1,2-diphenylethylene and α-methylstyrene.

Another preferred binder (C) is polybutadiene.

Other suitable binders (C) are selected from polyethylene oxide (PEO),cellulose, carboxymethylcellulose, polyimides and polyvinyl alcohol.

In one embodiment of the present invention, binder (C) is selected fromthose (co)polymers which have an average molecular weight M_(w) in therange from 50,000 to 1,000,000 g/mol, preferably to 500,000 g/mol.

Binder (C) may be cross-linked or non-cross-linked (co)polymers.

In a particularly preferred embodiment of the present invention, binder(C) is selected from halogenated (co)polymers, especially fromfluorinated (co)polymers. Halogenated or fluorinated (co)polymers areunderstood to mean those (co)polymers which comprise at least one(co)polymerized (co)monomer which has at least one halogen atom or atleast one fluorine atom per molecule, more preferably at least twohalogen atoms or at least two fluorine atoms per molecule. Examples arepolyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene,polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylenecopolymers, vinylidene fluoride-hexafluoropropylene copolymers(PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers,perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylenecopolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers andethylene-chlorofluoroethylene copolymers.

Suitable binders (C) are especially polyvinyl alcohol and halogenated(co)polymers, for example polyvinyl chloride or polyvinylidene chloride,especially fluorinated (co)polymers such as polyvinyl fluoride andespecially polyvinylidene fluoride and polytetrafluoroethylene.

Inventive electrodes may comprise 3 to 10% by weight of binder(s) (d),referring to the sum of component (a), component (b) and carbon (c).

A further aspect of the present invention is a battery, containing

-   -   (1) at least one cathode comprising inventive cathode active        material (A), carbon (B), and binder (C),    -   (2) at least one anode, and    -   (3) at least one electrolyte.

Embodiments of cathode (1) have been described above in detail.

Anode (2) may contain at least one anode active material, such as carbon(graphite), TiO₂, lithium titanium oxide, silicon or tin. Anode (2) mayadditionally contain a current collector, for example a metal foil suchas a copper foil.

Electrolyte (3) may comprise at least one non-aqueous solvent, at leastone electrolyte salt and, optionally, additives.

Nonaqueous solvents for electrolyte (3) can be liquid or solid at roomtemperature and is preferably selected from among polymers, cyclic oracyclic ethers, cyclic and acyclic acetals and cyclic or acyclic organiccarbonates.

Examples of suitable polymers are, in particular, polyalkylene glycols,preferably poly-C₁-C₄-alkylene glycols and in particular polyethyleneglycols. Polyethylene glycols can here comprise up to 20 mol % of one ormore C₁-C₄-alkylene glycols. Polyalkylene glycols are preferablypolyalkylene glycols having two methyl or ethyl end caps.

The molecular weight M_(w) of suitable polyalkylene glycols and inparticular suitable polyethylene glycols can be at least 400 g/mol.

The molecular weight M_(w) of suitable polyalkylene glycols and inparticular suitable polyethylene glycols can be up to 5,000,000 g/mol,preferably up to 2,000,000 g/mol.

Examples of suitable acyclic ethers are, for example, diisopropyl ether,di-n-butyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, withpreference being given to 1,2-dimethoxyethane.

Examples of suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.

Examples of suitable acyclic acetals are, for example, dimethoxymethane,diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.

Examples of suitable cyclic acetals are 1,3-dioxane and in particular1,3-dioxolane.

Examples of suitable acyclic organic carbonates are dimethyl carbonate,ethyl methyl carbonate and diethyl carbonate.

Examples of suitable cyclic organic carbonates are compounds of thegeneral formulae (II) and (III)

where R¹, R² and R³ can be identical or different and are selected fromamong hydrogen and C₁-C₄-alkyl, for example methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, with R² and R³preferably not both being tert-butyl.

In particularly preferred embodiments, R¹ is methyl and R² and R³ areeach hydrogen, or R¹, R² and R³ are each hydrogen.

Another preferred cyclic organic carbonate is vinylene carbonate,formula (IV).

The solvent or solvents is/are preferably used in the water-free state,i.e. with a water content in the range from 1 ppm to 0.1% by weight,which can be determined, for example, by Karl-Fischer titration.

Electrolyte (3) further comprises at least one electrolyte salt.Suitable electrolyte salts are, in particular, lithium salts. Examplesof suitable lithium salts are LiPF₆, LiBF₄, LiClO₄, LiAsF₆, LiCF₃SO₃,LiC(C_(n)F_(2n+1)SO₂)₃, lithium imides such as LiN(C_(n)F_(2n+1)SO₂)₂,where n is an integer in the range from 1 to 20, LiN(SO₂F)₂, Li₂SiF₆,LiSbF₆, LiAlCl₄ and salts of the general formula(C_(n)F_(2n+1)SO₂)_(t)YLi, where m is defined as follows:

t=1, when Y is selected from among oxygen and sulfur,

t=2, when Y is selected from among nitrogen and phosphorus, and

t=3, when Y is selected from among carbon and silicon.

Preferred electrolyte salts are selected from among LiC(CF₃SO₂)₃,LiN(CF₃SO₂)₂, LiPF₆, LiBF₄, LiClO₄, with particular preference beinggiven to LiPF₆ and LiN(CF₃SO₂)₂.

In a preferred embodiment of the present invention, electrolyte (3)contains at least one flame retardant. Useful flame retardants may beselected from trialkyl phosphates, said alkyl being different oridentical, triaryl phosphates, alkyl dialkyl phosphonates, andhalogenated trialkyl phosphates. Preferred are tri-C₁-C₄-alkylphosphates, said C₁-C₄-alkyls being different or identical, tribenzylphosphate, triphenyl phosphate, C₁-C₄-alkyl di-C₁-C₄-alkyl phosphonates,and fluorinated tri-C₁-C₄-alkyl phosphates,

In a preferred embodiment, electrolyte (3) comprises at least one flameretardant selected from trimethyl phosphate, CH₃—P(O)(OCH₃)₂,triphenylphosphate, and tris-(2,2,2-trifluoroethyl)phosphate.

Electrolyte (3) may contain 1 to 10% by weight of flame retardant, basedon the total amount of electrolyte.

In an embodiment of the present invention, batteries according to theinvention comprise one or more separators (4) by means of which theelectrodes are mechanically separated. Suitable separators (4) arepolymer films, in particular porous polymer films, which are unreactivetoward metallic lithium. Particularly suitable materials for separators(4) are polyolefins, in particular film-forming porous polyethylene andfilm-forming porous polypropylene.

Separators (4) composed of polyolefin, in particular polyethylene orpolypropylene, can have a porosity in the range from 35 to 45%. Suitablepore diameters are, for example, in the range from 30 to 500 nm.

In another embodiment of the present invention, separators (4) can beselected from among PET nonwovens filled with inorganic particles. Suchseparators can have a porosity in the range from 40 to 55%. Suitablepore diameters are, for example, in the range from 80 to 750 nm.

Batteries according to the invention can further comprise a housingwhich can have any shape, for example cuboidal or the shape of acylindrical disk. In one variant, a metal foil configured as a pouch isused as housing.

Batteries according to the invention provide a very good discharge andcycling behavior, in particular at high temperatures (45° C. or higher,for example up to 60° C.) in particular with respect to the capacityloss.

Batteries according to the invention can comprise two or moreelectrochemical cells that combined with one another, for example can beconnected in series or connected in parallel. Connection in series ispreferred. In batteries according to the present invention, at least oneof the electrochemical cells contains at least one electrode accordingto the invention. Preferably, in electrochemical cells according to thepresent invention, the majority of the electrochemical cells contain anelectrode according to the present invention. Even more preferably, inbatteries according to the present invention all the electrochemicalcells contain electrodes according to the present invention.

The present invention further provides for the use of batteriesaccording to the invention in appliances, in particular in mobileappliances. Examples of mobile appliances are vehicles, for exampleautomobiles, bicycles, aircraft or water vehicles such as boats orships. Other examples of mobile appliances are those which movemanually, for example computers, especially laptops, telephones orelectric hand tools, for example in the building sector, especiallydrills, battery-powered screwdrivers or battery-powered staplers.

The present invention is further illustrated by working examples.

EXAMPLES

The measurement of the onset temperature was performed as follows:

The respective electrochemical cell was first tested in a cyclingprogram: An electrochemical cell was charged to a given voltage with 0.1C in CC-CV mode and was held in a charged state until the currentdropped to at least 0.003 C. Then the electrochemical cell wasdischarged to 3V in CC mode. Then the electrochemical cell was againcharged to a given voltage in CC-CV mode and was held at the givenvoltage until the current has reached 0.003 C. Then, the respectiveelectrochemical cell was disassembled under an atmosphere of argon, andthe cathode composition was mechanically removed from the currentcollector.

An amount of 10 mg of cathode composition—cathode active material,conductive carbon and binder were then mixed with 3 mg of electrolyteE-2, consisting of a 1 M solution of LiPF₆ in ethylenecarbonate/dimethyl carbonate 1:1 by mass. The resulting slurry was thensubjected to differential scanning calorimetry over a temperature rangefrom 25 to 400° C., heating rate: 5 K/min. The results are shown in FIG.1.

I. Synthesis of Precursors

The term “solution” refers to aqueous solutions unless specifiedotherwise.

1.1 Synthesis of a Precursor TM-OH.1

A 9-I-stirred reactor with overflow for removing mother liquor wasfilled with distilled water and 36.7 g of ammonium sulfate per kg ofwater. The solution was heated to 45° C. and the pH value was adjustedto 11.6 by adding an aqueous 25 wt. % of sodium hydroxide solution.

The precipitation reaction was started by the simultaneous feed of anaqueous transition metal solution and an alkaline precipitation agent ata flow rate ratio of 1.84, and a total flow rate resulting in aresidence time of 7.7 hours. The transition metal solution contained Ni,Co and Mn at a molar ratio of 5:2:3 and a total transition metalconcentration of 1.65 mol/kg. The alkaline precipitation agent consistedof 25 wt. % sodium hydroxide solution and 25 wt. % ammonia solution in aweight ratio of 8.29. The pH was kept at 11.6 by the separate feed of 25wt. % sodium hydroxide solution. Beginning with the start-up of allfeeds, mother liquor was removed so that the liquid level in the reactorstayed constant. After 20.5 hours of precipitation, an aqueous solutionof 36.5 g of sodium aluminate per kg of water was added at a flow rateratio of 0.21 compared to the flow of transition metal solution, whilethe feed of transition metal solution was continued at the same rate.The feed of sodium hydroxide solution was reduced by 1.2%. The pH valueremained constant. After 26.5 hours all additions of solutions werestopped. Precursor TM-OH.1 was obtained by filtration of the resultingsuspension, washed with distilled water, drying at 120° C. in air over aperiod of 12 hours and sieving.

1.2 Precursor for Comparative Experiments C-TM-OH.2

The precursor for comparative experiments was a transition metalhydroxide of the formula Ni_(0.5)Co_(0.2)Mn_(0.3)(OH)₂ that was madewithout addition of sodium aluminate. It basically did not containaluminum hydroxide.

Precursor C-TM-OH.2 was dried at 120° C. in air over a period of 12hours.

II. Synthesis of Cathode Active Materials

II.1 Synthesis of a Cathode Active Material According to the Invention

Precursor TM.OH.1 was mixed with Li₂CO₃ so that the ratio of Li tometals other than lithium was 1.05 to 1. The mixture so obtained wasthen calcined in a muffle type furnace under the following conditions:

Heating Rate: 3 K/Min

300° C. 6 hours, 600° C. 6 hours, 920° C. 6 hours.

After the calcination program the material so obtained was cooled,deagglomerated in an agate mortar and sieved through a sieve with 32 μmmesh size.

Inventive cathode active material CAM.1 was obtained.

II.2 Synthesis of a Comparative Cathode Active Material

Precursor C-TM.OH.2 was mixed with Li₂CO₃ so that the ratio of Li tometals other than lithium was 1.08 to 1. The mixture so obtained wasthen calcined in a muffle type furnace under the following conditions:

From room temperature to 350° C. in 2.7 K/min hold at 350° C. for 4hours, from 350° C. to 650° C. in 1.3 K/min hold at 650° C. for 4 hours,from 650° C. to 900° C. in 1 K/min step, hold at 900° C. for 6 hours.

After the calcination program the material so obtained was cooled,deagglomerated in an agate mortar and sieved through a sieve with 32 μmmesh size.

Comparative cathode active material C-CAM.2 was obtained.

III. Making and Testing Electrochemical Cells

To produce a cathode (a.1), the following ingredients were blended withone another:

88 g of active materials 6 g polyvinylidene difluoride, (“PVdF”),commercially available as Kynar Flex® 2801 from Arkema Group, 3 g carbonblack, (c.1), BET surface area of 62 m²/g, commercially available as“Super C 65L” from Timcal,

3 g graphite, commercially available as KS6 from Timcal.

While stirring, a sufficient amount of N-methylpyrrolidone (NMP) wasadded and the mixture was stirred with an Ultraturrax until a stiff,lump-free paste had been obtained.

Cathodes were prepared as follows: On a 30 pm thick aluminum foil, theabove paste was applied with a 15 pm doctor blade. The loading afterdrying was 2 mA·h/cm². The loaded foil was dried overnight in a vacuumoven at 105° C. After cooling to room temperature in a hood discshapedcathodes were punched out of the foil. The cathode discs were thenweighed and introduced into an argon glove box, where they are againvacuum-dried. Then, cells with the cathode discs were built.

Electrochemical testing was conducted in “TC1” coin type cells. Theelectrolyte (c.1) used was a 1 M solution of LiPF₆ in ethyl methylcarbonate/ethylene carbonate (volume ratio 1:1).

Separator: glass fiber. Anode: lithium. Potential range of the cell: 3V-4.3 V.

C/5 5C Material Discharge/mA · h/g Discharge/mA · h/g C-CAM.2 163 126CAM.1 161 111

1. A process for making a particulate material of general formula (I):Li_(1+x)(Ni_(a)Co_(b)Mn_(c)M_(d))_(1−x)O₂   (I), wherein: x is in therange of from 0.015 to 0.03, a is in the range of from 0.3 to 0.6, b isin the range of from 0.05 to 0.35, c is in the range of from 0.2 to 0.5,d is in the range of from 0.001 to 0.03, and a+b+c+d=1, said processcomprising: (a) co-precipitating a mixed hydroxide of nickel, cobalt andmanganese from a solution of water-soluble salts of nickel, cobalt andmanganese by contacting such solution with a solution of alkali metalhydroxide; (b) adding an aqueous solution of an aluminate and therebyco-precipitating a layer of a mixed hydroxide of nickel and cobalt andmanganese and aluminium on the particles formed in step (a); (c)removing particles of (Ni_(a)Co_(b)Mn_(c)Al_(d))(OH)_(2+d) so obtainedand drying them in the presence of oxygen; (d) mixing the particlesobtained in step (c) with at least one Li compound selected from Li₂O,LiOH and Li₂CO₃; and (e) calcining the mixture obtained according tostep (d) at a temperature in the range of from 920 to 950° C.
 2. Theprocess of according to claim 1, wherein step (e) is performed in anoxygen-containing atmosphere.
 3. The process of claim 1, wherein informula (I): b is in the range of from 0.15 to 0.25, c is in the rangeof from 0.2 to 0.35, d is in the range of from 0.01 to 0.03, anda+b+c+d=1.
 4. The process of claim 1, wherein the duration of step (e)is in the range of from 3 to 12 hours.
 5. The process of claim 1,further comprising, between steps (d) and (e) at least one precalciningstep (e*) comprising: (e*) comprising heating the mixture obtained instep (d) at a temperature in the range of from 300 to 700° C. for aperiod of 2 to 24 hours, and performing step (e) with the materialobtained in step(s) (e*).
 6. A cathode active material, comprisingparticles of general formula (I):Li_(1+x)(Ni_(a)Co_(b)Mn_(c)M_(d))_(1−x)O₂   (I) wherein: x is in therange of from 0.015 to 0.03, a is in the range of from 0.3 to 0.6, b isin the range of from 0.05 to 0.35, c is in the range of from 0.2 to 0.5,d is in the range of from 0.001 to 0.03, a+b+c+d=1, wherein said Al ishomogeneously dispersed within said particles, and said particles havingan average particle diameter D50 in the range of from 5 to 12 μm.
 7. Thecathode active material according to claim 6, wherein in formula (I): bis in the range of from 0.15 to 0.25, c is in the range of from 0.2 to0.35, and a+b+c+d=1.
 8. The cathode active material according to claim6, having an onset temperature in the range of from 305° C. to 325° C.,wherein said onset temperature is measured by differential scanningcalorimetry (DSC).
 9. A cathode, comprising: (A) at least one cathodeactive material of claim 6, (B) carbon in electrically conductive form,(C) a binder material, and (D) a current collector.
 10. The cathodeaccording to claim 9, comprising: (A) 80 to 95% by weight the cathodeactive material, (B) 3 to 17% by weight of the carbon, and (C) 3 to 10%by weight of the binder material, percentages referring to the sum of(A), (B) and (C).
 11. An electrochemical cell, comprising containing atleast one cathode according to claim
 9. 12. The electrochemical cellaccording to claim 11, further comprising an electrolyte comprising atleast one flame retardant selected from the group consisting oftrimethyl phosphate, CH₃—P(O)(OCH₃)₂, triphenylphosphate, andtris-(2,2,2-trifluoroethyl)phosphate.